Textile yarn coated with cationic surfactant



United States Patent 3,168,416 TEXTILE YARN COATED WITH CATIONICSURFACTANT John D. Zech, Wilmington, Del., assignor to Atlas ChemicalIndustries, Inc, Wilmington, DelL, a corporation of Delaware No Drawing.Original application Apr. 23, 1957, Ser. No. 654,472, now Patent No.3,060,182, dated Oct. 23, 1962. Divided and this application May 15,1962, Ser. No. 194,966

Claims. (Cl. 117-1395) This application is a division of patentapplication Serial No. 654,472, filed April 23, 1957, and now UnitedStates Patent No. 3,060,182, granted October 23, 1962.

An object of this invention is to provide textile yarns having appliedthereto a novel class of cationic surfactants which contain basicnitrogen atoms and a plurality of hydroxyl groups.

An additional object of this invention is to provide textiles which aresoftened and lubricated.

The above objects of this invention, as well as additional objects, willbe apparent to those skilled in the art from a consideration of thefollowing description.

Briefly summarized, methods of preparing the treating agents of thepresent invention may involve the following steps:

(1) A polyhydric alcohol containing three or more hydroxyl groups permolecule, preferably a hexitol, is condensed with an epihalohydrin suchas, for example, epichlorohydrin.

(2) Separately, a polyalkylene polyamine is reacted with a fatty acid(or its equivalent) and also, if desired, with a short chain aliphaticacid (or its equivalent) under conditions producing carbon to nitrogenbonding. The reactants must be selected in such proportions that theresulting polyamine derivative contains residual basic nitrogen.

(3) The product of step (1) is brought into reaction with the product ofstep (2) in such proportions that from one to two basic nitrogenequivalents are present for each halogen equivalent, thus forming acationic surface-active salt which is a hydrohalide or a quaternaryhalide.

(4) If desired, the surface-active free base may be liberated bytreating the salt with an alkali. Thereafter, the free base may bereacted with various organic and inorganic acids including mineral acidssuch as, for example, phosphoric and sulfuric acid, to form other acidsalts which also have surface-active properties.

The initial step of the synthesis is exemplified by the condensation ofa polyhydric alcohol having three or more hydroxyl groups per moleculewith epichlorohydrin in the presence of a catalyst. The reaction can berepresented by the following chemical equation:

In the above equation x is a number of three or more and n is a numberfrom one to x. R is an hydroxyl-free radical of a polyhydric alcohol.When the polyhydric alcohol is a hexitol, from one to about three molsof epichlorohydrin are usually preferred.

The reaction illustrated above may be performed in the presence of anacidic catalyst as is well known in the prior art. Preferred catalystsare those of the Lewis acid type which include, for example, BF BFetherate, AlCl and SnCl but H 80 p-toluene sulfonic acid and the likemay also be used.

ice

The reaction may be carried out over a wide range of temperatureconditions. Below about 50 C. reaction times with higher polyhydricalcohols tend to become unduly long although reactions involvingglycerin can be readily performed at that temperature. Above about 130C. some polyhydric alcohols, for example hexitols, tend to undergoundesirable decomposition and color formation, but with less sensitivepolyhydric alcohols temperatures as high as 175 C. may be used. Apreferred temperature range is that between and 130 C.

The reaction may be performed at any convenient pressure. Whileatmospheric pressure is most convenient, the exact reaction conditionschosen are a function of the reactants used and the desired speed ofreaction. Thus, when the reactants are sorbitol (which solidifies atabout 90-95 C.) and epichlorohydrin (which boils at about 117 C.), it ispreferred to carry the reaction out at about 1l0 C. and atmosphericpressure.

While the reaction is generally carried out in the absence of solvent ordiluent, such materials may be used if desired to lower the viscosity,as an aid in controlling temperature, or to permit the use of lowertemperatures where high melting polyhydric alcohols (such as hexitols)are used.

Suitable polyhydric alcohols or mixtures thereof for use in thisconnection include, among others, triols (such as glycerol), tetritols(such as erythritol), pentitols (such as xylitol, arabitol, etc.), thehexitols (such as sorbitol, mannitol, dulcitol, etc.), polyhydricalcohols containing more than six hydroxy groups and polyhydric alcoholssuch as pentaerythritol, trimethylolethane, trimethylolpropane and otherpolymethylol alkanes.

Suitable polyhydric alcohols also include auhydro derivatives of otherpolyhydric alcohols (having at least three hydroxy groups per molecule)in which water has been removed from two hydroxyl groups to form acyclic ether, such as 1,4 sorbitan, and also external others ofpolyhydric alcohols, as, for example, diglycerol.

Another group of suitable polyhydric alcohols comprises themonosaccharides such as sorbose, mannose, glucose, arabinose and'xyloseas well as methyl glucoside and similar compounds.

The polyhydric alcohols useful in this invention include those, of thetype listed above, which have been modified by etherification withalkylene oxides such as ethylene oxide, 1,2 propylene oxide and mixturesthereof. As is well known in the art, such a reaction yields productscontaining polyoxy alkylene chains of varying length If a mixture ofalkylene oxides is employed, a given polyoxyalkylene chain may containboth the oxyethylene group and the oxypropylene groups. For the purposeof utilization in this invention the most suitable polyoxyalkyleneethers of polyhydric alcohols are those formed by reacting from one tosix mols of alkylene oxide with each mol or polyhydric alcohol. The termpolyhydric alcohol when used hereafter is intended to include all of theabove exemplified compounds and mixtures therof.

In lieu of epichlorohydrin other epihalohydrins may be used such asepibromohydrin nad epiiodohydrin. Other compounds such as 1-chloro-2,3epoxybutane and 2- chloro-3,4 epoxybutane are also suitable forproducing mono and polyhydroxy haloalkyl ethers of polyhydric alcohols.However, fluorine is not usually preferred for use in this connection,and consequently the halogen employed should preferably be one having anatomic weight above 30.

The condensation products of this reaction are, for the most part, veryviscous syrups. They are complex mixtures which may contain residualfree polyhydric alcohol in addition to various isomericepihalohydrinpolyhydric alcohol condensates (i.e., chlorhydroxypropylethers).

The following are a few specific examples of the initial (4) Formationof an imidazoline from the product of reaction which are intended toillustrate the process but Equation 2: not to limit it to the specificreactants involved. (H)

729 grams of anhydrous sorbitol were heated to a (I332 1320 reactiontemperature. ofbetween 98 and 108 (3.; 2.0 cc. H H of BF etheratecatalyst.(.45% BF were then added. I

Th a 925 f ichl roh d 011 ati .erea grams TYP o y mm m a r 0 Formationof a mono-amide from a propylene trisorbitol to epichlorohydrln of1:2.5) were added dropamine? I wise, over.a periodof 1 hour, 10 minuteswith-vigorous O H H stirring and control of cooling, so as to maintainthe H temperature-within thespecified limit. Thetemperature 2 2 wassubsequently-maintained for one hour between 98 H H and 108 C. by-theaddition of heat to insure completion O of the reaction. g E

Additional examples are given in Table I. In each case, the procedure;followed was similar to the-procedure /N-CH2?HNHCHz-CHN +Hz0outlined-above except aSlIldlCfl'tCd'lI'l/the table. H CH3 CH3 H Table IAlcohol Grams Grams Molal Ratio Co. of 45% Reaction EpichlorohydrinTotal Reaction Example No. Used Alcohol Epichloro- AlcoholzEpi. ,3'Temp., Ad'dn. Time Time hydrin Etherate C.

1-1 Sorbitol..- 729 925 112.5 2.0 98-108 2hrs.'.10 min. 1-21 do 051 5781:1.75 1.5 118-109. 1hr.45 min. I3 .110 1,184 602 1:1 3.0 97-109 1111338min. I-4 "do 1,200 1,220 1:2 .3.0 100-107 2.]1rs. 40 min 3hrs.40 min.1-.5- -do 913 1, 040 1:2. 2.0 100-107 2hrs.-0 min. 1-6- "do 91-3 5781:1.25 2.0 101-109 1 1hr. min. I7 do 1,184 3,160 1:5. 25 3.4 106-1154hrs.30 min 5hrs.30 min. 1-8. GlyceroL- 460 463 1:1 1.0 80-.105 min1hr.40min. 1-9 "do 400 698 11.5 1.25 92-107 53min 1hr; 53min.

1 Grams.

The second synthesis step is the carbon to nitrogen bond-formingreaction of a fatty acid (or its equivalent) witha polyalkylenepolyamine.

The chemistry of the amidation reaction between polyalkylene polyaminesand fatty acid has been well elucidated in the prior art. Undercomparatively mild reaction conditions, a carbon to nitrogen bond iscreated and simpleamides of the polyam-ines consequently are formed.Depending on the proportion of reactants the amides which are formed maybe mono-amides, diamides or higher amides. Under more severe conditions,particularly at hightemperatures, some of the first formed amidesundergo a ring closing dehydration to form substituted cyclic nitrogencompounds as, forexample, substituted imidazolines, and substitutedtetrahydropyrimidines.

The reactions involved may be illustrated by the following equationswherein R'COOH represents a fatty acid preferably containing from 12 to22 carbon atoms vper molecule.

(2) Formation of a mono-amide using diethylene triamine:

(6) Formationof an imidazoline from the product of .Equation 5 0 Bill HNO.Hz-OH-NHC H;.CH-N/ (5H3 I H (8) Formation. of a substitutedtetrahydropyrimidine from the product of Equation 7:

(9) Formation of a substituted imidazoline from the product of Equation3:

(10) Formation of a mono-amide from N-aminoethyl piperazine:

(10A) Formation of a di-amide from N-aminoethyl piperazine:

To prepare the intermediates of this step, a fatty acid preferablycontaining from 12 to 22 carbon atoms, such as, for example, lauric,tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic,dodecylenic, palmitoleic, oleic, ricinoleic, linoleic, linolenic,eleostearic, licanic, behenic, erucic or a naphthenic acid is broughtinto reaction with a polyalkylene polyamine. Mixtures of these acids mayalso be used.

Naturally occuring fats may be used in place of fatty acids. cottonseedoil, soybean oil, corn oil, castor oil, coconut oil and mixturesthereof. Mixtures of higher fatty acids derived from these fats, suchas, for example, coconut fatty acids, lard fatty acids and cottonseedfatty acids may also be used. Aliphatic mono-carboxylic acids derivedfrom petroleum by oxidation are also suitable.

Fatty acid esters, preferably lower alkyl esters, are also suitablereactants. When an ester is employed as the source of fatty acid, theby-product of the reaction is the corresponding alcohol instead ofwater. It may be removed by a distillation, if desired, or may be leftin the reaction mixture as a diluent. All of the above materials areintended to be included within the scope of the term fatty acidhenceforth.

It is also possible to modify the hydrophilic character of the productsof the invention by partially arnidating the polyamine with at least onemolecule of a long chain fatty acid of the type described above and alsoamidating other amino nitrogens with a short chain (2 to 6 carbon atomsper molecule aliphatic acid or its equivalent.

Thus, the product of Equation 2 may be reacted with a derivative of ashort chain aliphatic acid (i.e., ethyl acetate) as follows:

Suitable ones include, for example, tallow, lard,

The polyamines with which the above acids or acid equivalents arereacted are preferably polyethylene orpolypropylene polyamines, ormixtures thereof, containing from 3 to 5 amino groups. Suitablepolyamines include, among others, diethylene triamine, triethylenetriamine (N-aminoethyl piperazine), triethylene tetramine, tetraethylenepentamine, hydroxyethyl diethylene triamine (and other reaction productsof alkylene oxides such as ethylene and propylene oxide and polyalkylenepolyamines, provided however, that the resulting amine contain at leastone amino hydrogen), dipropylene triamine, tripropylene tetramine,tetrapropylene pentamine, compounds similar to 3,3 iminobispropylamineand mixtures of these compounds.

The proportion of reactants used must be such that the number of amineequivalents in the product exceed the equivalents of fatty acid by atleast one, thus giving the product basic characteristics. Use of excessamine favors the formation of such basic compounds. For instance, whereit is desired to obtain a product having a minimum of fatty acidsubstitution on the polyamine, such as the mono-amide of diethylenetriamine, an excess of polyamine is generally used. The excess amine canbe recovered by distillation and re-cycled to the process.

In connection with the basicity of the acylated polyamine it isimportant to remember that tertiary amino nitrogen atoms are incapableof amidation. Furthermore such tertiary amino nitrogen atoms exhibitbasic characteristics. Therefore, even if a polyamine which containstertiary amino nitrogen is fully amidated it still has basic propertiesafter amidation because the tertiary amino nitrogen has not beenconverted to an amido nitrogen. Tertiary nitrogen atoms thus remainbasic throughout the reaction and are counted as part of the excessamine equivalents in selecting the reactant proportions.

In the subsequent formation of the surfactants of this invention eitherthe open chain amide type of derivative or the cyclized type, asexemplified by the substituted imidazolines and substitutedtetrahydropyrimidines may be used. Mixtures of the two types ofderivatives may also be used. In the employment of the novelcompositions of the invention it usually is not of moment whether theamide or the cyclic type of configuration is present in the molecule.

When it is desired that the open chain amide structure be predominant,the reaction is carried out at relatively low temperatures, usually fromabout to 180 C. and for short times, of about /2 to 4 hours. Highertemperatures and/or longer times favor conversion to the imidazolinetype products. Reaction temperatures up to 275 C. and times up to 10 ormore hours may be utilized.

Examples II-l to II-11 illustrate the preparation of fattyacid-polyamine derivatives suitable for use in producing thecompositions of the invention. I

EXAMPLE II-l 103 grams (one molar proportion) of diethylene triamine and568 grams (two molar proportions) of a commercial stearic acid werecharged into a reaction flask and heated for one hour at a temperatureof from to C.

During the course of the reaction 40 ml. of distillate were removed fromthe flask. The product contained 6.4% nitrogen and had, as determined bytitration, an HCl equivalent of 586. The predominant component was thedi-stearic acid amide of diethylene triamine.

EXAMPLE II-2 128 grams (1.2 5 mols) of diethylene triamine and 731 gramsof tallow (2.5 acid equivalents) were heated together for 4 hours in thetemperature range of 138 to 174 C. after which 26 grams of vacuumdistillate were removed by vacuum stripping at 1 mm. The contents of theflask solidified at room temperature to a waxy solid consistingprincipally of the tallow acid di-amide of diethylene triamine. A smallproportion of glycerol liberated from the fat used as a source of fattyacid remained with the product. The overall nitrogen content was 5.91%and the HCl equivalent was 704.

EXAMPLE II-3 256 grams of diethylene triamine and 1646 grams of tallowwere heated together at 150 to 175 C. for 3 hours and 40 minutes. Duringthe heating which was conducted under a vacuum, 57 grams of distillatewere collected. The residue in the flask-comprised the tallow acidamides of diethylene triamine. The nitrogen content of the mixture was5.5% and the HCl equivalent was 780.

EXAMPLE II-4 The preparation of Example II-3 was repeated except thatonly 1280 grams of tallow were employed and the heating time was 3 hoursand 30 minutes. The nitrogen content of the resulting product was 6.86%and its HCl equivalent was 544. The product contained a mixture oftallow acid mono-and di-amides of diethylene triamine.

EXAMPLE 'II5 The preparation of Example II-3 was repeated except that1462 grams of tallow were employed. The product, comprising principallythe tallow acid di-amide of diethylene triamine had a nitrogen contentof 5.97% and an HCl equivalent of 712.

EXAMPLE 11-6 EXAMPLE II-7 350 grams of lard and an excess (600 grams) oftriethylene tetramine were heated together for hours while thetemperature rose from 191 to 262 C. The reaction product was thenstripped under vacuum to 249 C. at 1 mm. pressure. The resulting productcontained a mixture of l-(aminoethyl iminoethyl), 2-alkyl imidazolineand the lard acids amide thereof, and related compounds, Where an alkylstands forthe mixed carboxyl-free radical of lard acids. The nitrogencontent was 12.2% and the HCl equivalent was 19-1.

EXAMPLE 11-8 376 grams of diethylene triamine and 300 grams .of coconutoil were heated together for 4 hours and the temperature held at from179 to 256 C. The product was vacuum stripped to 162 C. at 1 mm.pressure yielding a mixture of l-aminoethyl, v2-alkyl imidazoline andthe coconut fatty acid amide thereof, alkyl representing the mixedcarboxyl-free residues of the coconut fatty acid. The nitrogencontent ofthe composition was 13.9% and its HCl equivalent was '162.

EXAMPLE H-9 400 grams of commercial stearic acid (Wilmars 501 acid) and700 grams of tetraethylene pentamine were heated together for 5% hourswhile the temperature was raised :to the range from 180 to 261 C. Thereaction mixture was stripped to a temperaturefof 233 C.

(8 at a pressure o'f 0.5 mm. to yield a product havinga nitrogen contentof 15.3% and an -HCl equivalent of 146.

EXAMPLE II-10 201 grams of 'N-hydroxyethyl diethylene triamine (made byreacting one mol of ethylene oxide with one mol of diethylene triamine)and 386 grams of oleic acid were heatedtogether forl hour and 50 minutesat 150 to 170 C. The product was then reacted with 310 cc. of ethylacetate at 87 C. to further amidate it with the equivalent of a shortchain aliphatic acid. Unreacted ethyl acetate and formed volatileby-products of the reaction were removed by distillation leaving aproduct consisting essentially of the acetic amide of the oleic acidmono amide of N-hydroxyethyl diethylene triamine. Its nitrogen contentwas 8.89% and its HCl equivalent was 411. This reaction can also beperformed using acetic acid instead of ethyl acetate.

EXAMPLE 11-11 2,750 grams of inedible tallow and 481 grams of diethylenetriamine were heated together at 150 C. for 3 hours under a nitrogenatmosphere. The product, amounting to 3215 g., was a tan colored waxymaterial with a Gardner color of 10, and HCl equivalent of 653, and anitrogen content of 5.93%.

The third step in the synthesis of the hydroxyl-bearing cationicsurfactants of the present invention is the reaction of the.polyol-epihalohydrin ethers of step 1) with the fatty acid-polyalkylenepolyamine derivatives of step (2) to form salts.

The products are cationic in nature and may be characterized as salts ofsecondary amines, tertiary amines and quaternary ammonium bases. Whenthe polyaminefatty acid derivative has basic characteristics dueonly toa tertiary amino nitrogen atom then the salts formed in this reactionwill be quaternary ammonium salts. In any event all the product formedin this synthesis step contain pentavalent nitrogen. In the case of thequaternary salts, four of the valence bonds of the nitrogen aresatisfied bycarbon whereas in the case of the secondary and tertiaryamine salts respectively, only two and three of the bonds are sosatisfied.

The reactant proportion are preferably so selected that from 1 to 3, andmore preferably from 1 to 2, base equivalents of the fattyacid-polyalkylene polyamine derivatives are condensed per halogen atomof the polyol epihalohydrin ether. The reaction may be carried out atany temperature from about 75 to 150 C., the preferred range being fromto C. The following equations, in which the symbols have the samemeaning as above, are illustrative of the type of salts which may beformed from the several types of intermediates hereinbefore described.

(12) Reaction involving an amino-amido and a hexitolepichlorohydrinderivative:

( 13) Reaction involving an amino-substituted imidazoline and ahexitol-epihalohydrin derivative:

(14) Reaction involving product of Equation 8 and a hexitolepichlorohydrin derivative:

R CH2 CH (15) Reaction of product of Equation 9, which contains tertiaryamino nitrogen, and a triol-epichlorohydrin derivative to form aquaternary ammonium salt:

pendently selected from the groups exemplified by the following:

( y zyN B yH2yNB)bE and substituted imidazoline and tetrahydropyrimidinederivatives of (a) such as, for example:

( yHay Fh CyH2y0H (CyHflyNF)cG Wherever used in the above radicals:

a and b are integers (either of which may be zero) whose total is awhole number from 2 to 4;

Each 0 is an integer from zero to 4 whose total value in a given radicalis a number between 2 and 4;

Each d is an integer from zero to 2 provided that their total in a givenradical does not exceed 2;

e is an integer from 1 to 3;

y is either 2 or 3;

Each B is independently selected from the group consisting of hydrogen,hydroxy lower alkyl, acyl radicals of fatty acids containing from 1 2 to22 carbon atoms and acyl radicals of aliphatic acids containing from 2to 6 carbon atoms;

D is the hydrocarbon radical of an acyl variant of Each E isindependently selected from the group consisting of hydrogen andhydroxyl lower alkyl;

Each F is independently selected from the group consisting of hydroxyllower alkyl, acyl radicals of fatty acids containing from 12 to 22carbon atoms and acyl radicals of aliphatic acids containing from 2 to 6carbon atoms;

Each G is independently selected from the group consisting of hydroxylower alkyl and amino hydrogen; and

Bach I is independently selected from the group consisting of acylradicals of fatty acids containing from 12 to 22 carbon atoms and acylradicals of aliphatic acids containing from 2 to 6 carbon atoms;

Provided finally that in a given radical at least one of B, D, F, or Imust be long chain acyl.

After compounds of the above type have been synthesized, they may bereacted if desired with watersoluble, amine-salt-forming acids. It isthus possible to form nitrates, sulfates, alkyl sulfates and phosphatesas well as organic acid salts such as formates, acetates, lactates,tartrates, benzene or toluene sulfonates and citrates.

The following examples show in detail the preparation of cationicsurface-active agents in accordance with the invention. The examples areillustrative but are not to be considered as limiting the invention.

EXAMPLE IH-l 318 grams of the product of Example II1 and 92 grams of theproduct of Example 1-8 were heated together for 1 /2 hours in thetemperature range of to 126 C. The resulting condensate was a softwater-dispersible wax with marked surface active properties. Additional11 examples are present in Table 11 which indicated the amounts ofreactants, reaction conditions and natureof the resulting products.

12 of 4was assigned to these samples. The panels evaluation of theeffect of compounds of theiuvention upon samples of the staple fibersare given in Table III.

Table II F. A.-Polya1nine Polyol-Epichlor. Example Reaction Reaction N0. Time, Temp, Nature of Product Wt.- From Wt.- From Hrs. 0. grams Ex.No. grams Ex. No.

1II-2 200 11-2 56 1-2 2 77-125 Soft, water-soluble wax. 11I-3 300 11-363 1-5 2 90-125 Soft, water-dispersible wax. 1I14 316 11-3 92 I-6 290-126 Do. 111-5-.-" 300 11-4 125 I-G 2 100-130 D0. III-6"- 300 11-4 91.1-5 2 78-132 Do. 111-7-.- 186 11-2 45. 5 I-5 2% 100-131 D0. 111-8 30011-5 95 1-6 2% 77-126 D III-0- 300 11-5 69 1-5 2% 68-132 D 0. I11-10 23311-6 92 1-4 2 99-117 Do. 111-11.-" 193 11-7 278 1-3 1% 87-136 Waxywater-soluble SOlld, dispersible in-alkali. 111-12.--- 174 11-8 256 1-61% 84-128 Do. III-13"" 174 11-9 213 I-6 1% 89-122 Do. 1I1-14 231 11-10111 I-2 3% 82-110 Soft water dispersible wax,

dispersible'in alkali. I1I-15 210 11-10 166 1-1 2% 100-117 Do.111-16.-.. 430 11-11 121 1-8 6 115-122 Soft, brown 'water dlspersiblewax. 11I-17 430 11-11 103 I-9 6 116-118 Soft, brown readily waterdispersible wax.

Compounds of this invention also have utility as textile softeners andlubricants. When used as a softener, they give a soft, pleasing feel tofabrics which would otherwise tend to feel stiff and harsh. When used asa lubricant, during textile processing, they reduce friction betweenmoving yarn and metal machine parts over which it moves. Cationic amidesof the invention are generally preferred for this use.

A series of tests were made to demonstrate the effectiveness of thesecompounds as textile treating agents. In each case, the procedurefollowed was the same.

Five gram batches of ten different staple fibers, including cotton,nylon, Vicaraf Acrilan,* Orlon,* Dacron, acetate, Dynel,* rayon, andDarlan (*indicatesatrademarked product. For manufacturer and nature ofthese fibers, see standard reference works such as The CondensedChemical Dictionary, th ed., Reinhold, 1956). were each immersed in 300cc. of a 0.5% aqueous solution of the treating agent to be tested. The.temperature of the solution was 50 C. After three minutes, the staplefiber was centrifuged for thirty seconds, allowed to dry and thencarded. Samples were evaluated by a panel.

A rating scale of l to 5 was used. To establish a'basis of comparisonfor the evaluation, a sample of each staple was treated with cetyl ethylmorpholinium ethosulfate in the manner indicated above and each .ofthese samples was given an arbitrary rating of 2 on the above scale. Anadditional sample of each staple was then treated in the above mannerwith anyalkyl biguanidine and a rating After the evaluation wascomplete, the staple fiber was placed in an oven and kept at 120 C. for16 hours to determine if heat had any etfecton the color. An asterisknext to a value in Table 111 indicates that discoloration occurred-onheating.

To determine lubricity, rayon skeins were treated with 300 cc. of 0.5%aqueous-solution of the various agents at 50 C. The rayon skeins werethen centrifuged for 30 seconds, air dried and finally stored at aconstant temperature and 50% relative humidity for '16 hours to allowthem to reach equilibrium moisture conditions. At the end of that time,and under the same controlled temperature and humidity, frictionmeasurements were made. Yarn to metal friction was measured at a yarnspeed of meters per minute and yarn to yarn friction was measured at l'centimeter per minute. Lubricity measurements are also recorded in TableIII. Whereas ordinary rayon to metal tension without lubricants is onthe order of 1.25 grams, the tensions after treatment were all below 70grams.

When .the product is used as. a lubricant, it may be removed by scouringafter the conclusion of textile processing. If it is used as a softener,it will be removed gradually in the course of several launderings.

The treating compound is usually applied in an aqueous dispersion. Itmay be applied in several ways, including the use of a dipping roll, byimmersion of the material to be treated in a bath, by use of a padderand in other similar manners. The application may come at the beginning,or end of the textile .process and is often followed by a dryingoperation.

Textile treatment Relative Staple Softness Friction-grams Product Exam.No. of

Example Nylon Vicara Acrilan Orlon Dacron Acetate Dyncl Rayon DarlauCotton Avg. Yarn to Yarn to Yarn Metal Many changes in processingdetails may be made without departing from the principles set forthherein and the invention is to be broadly construed in accordance withthe following claims.

What is claimed is:

1. A textile yarn having applied thereto a cationic surfactant preparedby reacting at a temperature from about 75 to 150 C. a reactant (1)represented by the formula:

wherein R is a hydroXyl-free radical of a polyhydric alcohol, X is ahalogen atom having an atomic weight greater than 30, x is a number from3 to 6 and n is a number from 1 to x, with a second reactant (2) a basicamino nitrogen containing compound which is a higher fatty carboxylicacylation product of a polyalkylene polyamine which polyamine has from 3to 5 amino groups.

2. A textile yarn in accordance with claim 1 wherein x is 6 and n is anumber from 1 to 4.

3. A textile yarn in accordance with claim 2 wherein R is ahydroxyl-free radical of sorbitol and the second reactant is a C to Cfatty acid diamide of diethylene triarniue.

4. A textile yarn in accordance with claim 3 wheren X is chlorine.

5. A textile yarn in accordance with claim 4 wherein n is about 2 andthe second reactant is a tallow acids diamide of diethylene triamine.

References Cited in the file of this patent UNITED STATES PATENTS2,197,930 Jackson et al Apr. 23, 1940 2,198,001 Dickey Apr. 23, 19402,199,989 Dickey et a1. May 7, 1940 2,277,788 Shipp et a1 Mar. 31, 19422,878,273 Conbere et a1 Mar. 17, 1959 2,904,454 Berndt et al Sept. 15,1959 3,003,954 Brown Oct. 10, -l961 3,074,815 Lee et a1. Jan. 22, 196 3

1. A TEXTILE YARN HAVING APPLIED THERETO A CATIONIC SURFACTANT PREPAREDBY REACTING AT A TEMPERATURE FROM ABOUT 75* TO 150*C. A REACTANT (1)REPRESENTED BY THE FORMULA: